WO2014161973A1

WO2014161973A1 - Method for removing fluorinated organic compounds from contaminated fluids, and adsorbent component and adsorbent kit used therefor

Info

Publication number: WO2014161973A1
Application number: PCT/EP2014/056761
Authority: WO
Inventors: Stefano Bruzzano; Martin Cornelsen
Original assignee: Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V.; Cornelsen Solutions GmbH
Priority date: 2013-04-05
Filing date: 2014-04-03
Publication date: 2014-10-09
Also published as: DE102013206066A1; US10196286B2; EP2981508A1; EP2981508B1; US20160046506A1

Abstract

The invention relates to a method for removing fluorinated organic compounds from contaminated fluids by means of a kit that comprises a first and a second adsorbent component, or only by means of the first adsorbent component alone. First, the first and optionally the second adsorbent component are provided. The second adsorbent component is a solid adsorbent; the first adsorbent component is a chemical compound that contains a lipophilic group and a hydrophilic group, or contains such a compound in dissolved form, wherein the hydrophilic group contains at least one cationic group and wherein the lipophilic group is selected from alkyl groups that comprise at least one octylene unit, from aryl groups, and from aralkyl groups. Thereafter, the contaminated fluid is brought in contact with the first adsorbent component, and optionally the fluid is also brought in contact with the second adsorbent component. Finally, the adsorbent component(s) are removed from the fluid together with the adsorbed fluorinated organic compounds. The invention further relates to the kit required for said method.

Description

Patentanmeldung: Process for the separation of fluorinated organic compounds from contaminated fluids and adsorbent used for this purpose and

Adsorbent Kit Applicant:

Fraunhofer-Gesellschaft for the promotion of applied research e.V.

The application relates to a method which is particularly suitable for the separation of fluorinated organic compounds from fluids, a kit which can be used for this purpose and a usable, in particular soluble, first adsorbent component having a lipophilic group and a hydrophilic group. Here, on the one hand, contacting of the contaminated fluid takes place at least with the first, generally amphiphilic, adsorbent component. Subsequently, a contacting with a second, solid adsorbent component can take place, which allows adduct formation, so that the loaded adsorbent can be separated from the purified fluid. Fluorinated organic compounds have excellent and unique technological properties, which is why they have long been used in many different industrial products and processes (eg as textile and paper equipment, as water and dirt repellent coatings, as hydraulic fluids, as fire-extinguishing foams, in the Teflon production and in the electroplating). Due to their specific properties, these substances are often without alternative for many applications. However, fluorinated compounds, in particular perfluorinated surfactants, have an ecotoxic as well as a human toxic potential, which is based inter alia on the high tendency to bioaccumulate. Due to their high persistence, perfluorinated surfactants have been ubiquitously detectable in the environment for several years. They are essentially released by effluents from fluorochemical production processes or by the use and disposal of the corresponding products into the environment. For example, perfluorinated surfactants can be mentioned here as foam formers in fire-extinguishing foams, as well as wetting agents and antifoggants in galvanic, phototechnical or semiconductor technology companies. In the chemicals legislation and guidelines of many countries, such as the European Directive 2006/122 / EC has been made aware of the dangers of perfluorooctanoic acid and perfluoroalkylsulfonic and strongly restricted their use. However, in a number of industrial companies perfluorinated surfactants are indispensable, especially in electroplating, in fire protection and in photo and semiconductor technology; therefore exceptions for these purposes have been included in recent legislation. For example, these substances are used in electroplating in occupational safety (antifogging and wetting agents); to

Immobilization of the very toxic and carcinogenic chromic acid they are used as a foam barrier or spray inhibitor.

In order to reduce an input of fluorinated organic compounds, in particular highly toxic compounds such as special perfluorinated surfactants (PFT) in wastewater and groundwater, various measures are implemented in the companies today. In particular, the separation and separate disposal of polluted with these substances wastewater streams should be mentioned. Of crucial importance for this is the use of different treatment methods of wastewater and

Groundwater remediation.

The problem with cleaning, however, is that, in particular, perfluorinated surfactants can not be effectively separated either by conventional biological processes or by classical physical methods such as stripping from contaminated fluids due to their chemical-physical properties.

For example, US 2007/01381 10 A1 describes the removal of perfluorinated surfactants by means of capacitive deionization of contaminated waters. However, this method is too costly for the purification of large amounts of wastewater in terms of purchase, operation and maintenance of the equipment. Similarly, this also applies to wet-oxidative methods, eg. B. by means of UV, ozone, peroxide or microwave radiation. In some physical separation processes such as membrane technology, after treatment, highly concentrated aqueous solutions are present as wastes whose (thermal) disposal is difficult and thus uneconomical.

Among the chemical separation processes, in particular adsorption methods are mentioned. For example, adsorber resins are used to purify wastewater. They show a very selective adsorption capacity and a high adsorption capacity in the range of high pollutant concentrations. For example, the

WO 2008/066748 A1 the use of ion exchange materials. Nevertheless adsorber resins could not assert themselves as adsorptive for the treatment of waste water and groundwater. Compared to activated carbon, they are more expensive and more expensive to regenerate.

Therefore, the adsorption on activated carbon is often used for the purification of PFT-containing wastewater. However, fluorinated surfactants, in particular short-chain perfluorinated surfactants, can not be removed selectively hereby.

For example, EP 1 561 729 A1 discloses an adsorption method based on activated carbon in order to obtain fluorinated emulsifiers in a waste water containing particles

Contains fluoropolymers, separate. These are the wastewater before the

Activated carbon adsorption non-ionic or anionic surfactants added to prevent the deposition of polymer particles on the activated carbon and thus clogging of the filter.

It is thus an object of the present invention to overcome the disadvantages of the prior art and to provide an adsorbent and a process for the use of additives for the separation of fluorinated organic compounds, in particular fluorinated or perfluorinated surfactants, from contaminated fluids, which has the disadvantages of the prior art technology overcomes.

These objects are achieved by the subject matter of the independent claims. Further embodiments and further developments are the subject of dependent claims and continue to be apparent from the following description. According to the invention, it has been recognized that fluorinated organic compounds can be separated from fluids at least by means of a kit comprising a first adsorbent component and a second adsorbent component, in particular the separation of perfluorinated organic compounds and / or fluorinated surfactants from fluids contaminated therewith. However, in some embodiments, even using only the first adsorbent component is sufficient to separate these substances.

The first adsorbent component is a chemical compound containing a lipophilic group and a hydrophilic group (and hence an amphiphilic chemical compound) wherein the hydrophilic group contains at least one cationic group. The chemical compound containing a lipophilic group and a hydrophilic group can be present under normal conditions as a liquid or in solid form and for the use of the method according to the invention (for example by means of a solubilizer) are brought into a dissolved form, this training is sufficient a solution in the fluid to be purified. In this case, a dissolved form is also understood as meaning that at least one weight fraction of the first adsorbent component which corresponds to 10% by weight of the fluorinated organic compounds present in the contaminated fluid is present in dissolved form in the contaminated fluid. Often, however, a complete dissolution will take place. For presence in dissolved form, according to the invention, micelles formed in the fluid are always counted. The solubility can therefore be determined in a simple manner by determining the amount of unresolved first adsorbent component. In the case of a solution for the method according to the invention then so be used a first adsorbent component, in which the amphiphilic chemical compound in a

Solvent is present dissolved or can be dissolved in an example to be cleaned aqueous fluid.

A lipophilic group in the first adsorbent component is understood to mean that the structure contains at least one of the following groups: an alkyl group which contains at least one octylene unit (ie a unit of the formula -C ₈ H ₁₆ -, ie an octyl radical or not) terminal alkyl group, for example, an octylene group substituted with the hydrophilic group), or alternatively, an aryl group or an aralkyl group. Due to the specific structure of the structure of the first adsorbent component, this can effectively act as a carrier compound; for the substances to be separated, a tailored adjustment of the interactions additive / fluorinated organic compound can be carried out so that the formation of an adduct occurs, which can be subsequently separated by means of the second Adsorbenskomponente or precipitates without addition of the second Adsorbenskomponente from the fluid to be cleaned (wherein with precipitation According to the invention, in addition to sedimentation, in particular also flocculation and flotation is understood). For the first adsorbent component, a range of simple starting materials may be used, for example, commercially available surfactant structures, which are well known to those skilled in the art in general and in the fields such as detergent, paper, food and water chemistry in particular.

The optional second adsorbent component is a conventional solid adsorbent, that is, a substance which, because of its large, active surface, is capable of selectively enriching (ie, adsorbing) chemical compounds to be separated from gaseous or liquid mixtures at its interface. The second adsorbent component is therefore often referred to according to the invention as "solid adsorbent component". In particular, adsorbents which are also suitable as a stationary separation phase and with which the separation of fluorinated compounds, in particular fluorinated surfactants, can in principle be used as the second adsorbent component. Such adsorbents have been known to the skilled person for a long time. According to the invention, it has been observed that the effect of the solid adsorbent component is supplemented or intensified by the first adsorbent component.

Under solid is understood in the solid adsorbent component that this component does not dissolve in the contaminated fluid. The same applies to an optionally present solvent, which is responsible for the conversion of a solid amphiphilic chemical compound in the liquid state, that is for the

Provision of a first adsorbent component is required. Even in such a solvent, the solid adsorbent component does not dissolve. A solution to the above problem is therefore provided by the following

Process according to the invention using the first adsorbent component: First, in a step A), the first adsorbent component is provided.

Subsequently, in step B), the contacting of the contaminated fluid with the first adsorbent component takes place. Finally, in a step D), the at least first adsorbent component with the adsorbed fluorinated organic compounds is separated from the fluid.

According to the invention it has been found that by means of such a method by contacting a contaminated fluid with a carrier compound, namely the first adsorbent component, a very selective separation of fluorinated organic

Compounds, in particular fluorinated or perfluorinated surfactants is possible. Without wishing to be limited to this, it is assumed that this observation is based on the following model concept:

In step B) there is an interaction between the fluorinated organic compound to be separated and the first adsorbent component, wherein the

Interaction between the two substances is so strong that one is the first

Adsorbent component may also be referred to as a carrier compound. Will the

Concentration of the first adsorbent component in the fluid chosen to be large enough, so may advantageously a micelle formation of the amphiphilic first

Adsorbent component done; the fluorinated organic compound to be separated can then optionally also be arranged inside the micelle. The first

Adsorbent component is further chosen so that either precipitates due to their solubility properties by adduct formation with the substances to be separated from the fluid or adduct formation by addition of the second

Adsorbent component is precipitated.

Finally, in step D), the adduct of amphiphilic first adsorbent component and fluorinated organic compound or in the case of those described below

Embodiment with second adsorbent component, the adduct of amphiphilic first adsorbent component, second adsorbent component and fluorinated organic compound are separated from the contaminated fluid. This is possible, for example, by means of sedimentation or filtration. With the method according to the invention, the first adsorbent component and the kit consisting of the first adsorbent component and the second adsorbent component, a method is now made available with which inexpensive fluorinated organic

Compounds, in particular perfluorinated surfactants, can be separated from contaminated fluids. By interaction of the amphiphilic chemical

Bonding via the lipophilic groups, on the one hand, and existing cationic charge, on the other hand, causes the formation of an adduct which either precipitates spontaneously but at least exhibits better adsorption on the solid adsorbent component (eg activated carbon) than the pure fluorinated organic compound. Furthermore, it has been shown that the method according to the invention is not only suitable for the separation of perfluorinated or partially fluorinated surfactants, but also for perfluorinated compounds in general (which can be separated well owing to the interaction with the hydrophobic groups) as well as fluorinated other organic compounds ( such as organic compounds having fluorinated alkyl groups or fluorinated aromatic compounds, which in turn may be more readily adsorbed by the hydrophobic groups). Particular mention should be made of fluoroalkylalkanols or fluoroalkylalkanediols, fluoro-alkyldimethylbetaines, fluoroalkylethylbetaines, perfluorinated and partially fluorinated fatty acid esters, perfluorinated and partially fluorinated fatty alcohol sulfates, perfluorinated and partially fluorinated fatty alcohol polyglycol ether sulfates, nonionic polymeric fluorinated surfactants, aliphatic partially fluorinated polymer esters and perfluoroalkylbetaines.

The process according to the invention is also suitable for the separation of other undesirable substances from fluids, in particular anionic substances, which interact with an optionally contained cationic group and can be separated thereby. These include in particular uranyl compounds or inorganic or organic arsenates and antimonates.

The inventive method, the first adsorbent component and the

Finally, kits according to the invention are suitable not only for the purification of contaminated waters but also for other liquids, such as organic solvents (if no chemical reaction of the solvent with substituents of the first

Adsorbent component takes place). Furthermore, in principle, the purification of gases, in particular of air, possible, however, is designed in a multi-stage

Adsorption process, the process management significantly more difficult than with liquids. Optionally, the first adsorbent component and the kit according to the invention can also be used for the enrichment of valuable substances, for example particularly expensive fluorine-containing compounds; Such recyclables can in one

Desorption be recovered below.

As stated above, the first adsorbent component used according to the invention contains a lipophilic group. This comprises either an alkyl group, an aryl group and / or an aralkyl group. The alkyl group may be an octyl unit or contain an octylene unit. With even longer alkylene or alkyl groups, the lipophilicity can be further increased, which may be advantageous for certain fluorinated organic compounds to be separated. Thus, as a lipophilic group, for example, a decylene unit or decyl unit can be used or a

Dodecyl unit or dodecylene unit. Suitable aryl groups are, in particular, phenyl groups or phenylene groups which are unsubstituted or may also be substituted (here again, in particular, with further pure ones

Hydrocarbons in aromatic or aliphatic form). Suitable aralkyl groups are, for example, benzyl groups. The aralkyl groups, for example the benzyl or benzylene groups, may be substituted or unsubstituted. Benzylene groups in which the ionic group is bonded to the aromatic ring are also conceivable. In order to enhance the interaction with the fluorine-containing compounds to be adsorbed, the alkyl group, aryl group or aralkyl group may also be partially fluorinated or perfluorinated. In particular, partially fluorinated or perfluorinated alkyl or alkylene units are to be mentioned in these groups.

In order to achieve that the first adsorbent component already precipitates out of the fluid by adduct formation with the substances to be separated off, the first adsorbent component should in particular be selected such that-depending on the fluorine-containing compound to be separated-an adduct with low water solubility is formed. In principle, this is already achieved by the abovementioned alkyl, aralkyl or aryl groups. However, this effect can be exacerbated if already (based on the fluorine-containing compounds to be separated) equimolar amount of the first

Adsorbent component (even at concentrations less than 1 μηηοΙ / Ι) without one

Solubilizer is not completely soluble in the fluid. Irrespective of this, compounds which have at least two alkyl, aralkyl or aryl groups as defined in the preceding paragraph and / or an alkyl radical having at least one tetradecylene unit, but in particular compounds which have at least two, are also suitable for enhancing these properties Contain groups with tetradecylene units.

In general, a "cationic group" of the first adsorbent component in the context of this application is to be understood as meaning that this group is always cationic in a given fluid or, alternatively, is present as a cation only under certain conditions. Thus, especially with aqueous fluids, the cationic group may be at least partially in the protonated form at higher pHs in the neutral form and only at lower pHs, as is often the case with primary, secondary or tertiary amines. It is essential then that even in a given contaminated fluid the cationic group is present to a certain extent in the protonated form. Thus, primary, secondary and tertiary low molecular weight amines have a pk _B of about 4 in water. As a rule, the protonated form is predominantly present in pH neutral waters. Only in strongly alkaline waters can the protonated fraction be significantly lower. However, it should be at least 1%, preferably at least 10%. In order to achieve a more effective adsorption, with such cationic groups, a pretreatment of the contaminated waters can take place, in which the pH is lowered.

According to the invention, the cationic group contained in the first adsorbent component may in particular be an ammonium ion, usually an organically substituted ammonium (frequently using the hydrophobic group as the "organic substituent" of the

Ammonium), but it may also be a primary, secondary or tertiary amine. Optionally, quaternization may be carried out in primary, secondary or tertiary amines in a modification reaction to form at least partially quaternary amine groups. Furthermore, the cationic group may also be a phosphonium ion and here again in particular an organically substituted Phosphonium (usually using the hydrophobic group as an organic substituent). Finally, the cationic group can also be present in the form of a metal complex, for example a transition metal complex (in this case, a

Linkage with the hydrophobic group also be present in the metal complex, with this being a whole range of possibilities; for example, the hydrophobic group may be part of a ligand of the metal complex or else the ligand itself). In individual cases, the cationic group can also in one

zwitterionic compound, for example a betaine structure

(In particular, carbo-betaines and sulfo-betaines are to be mentioned with an ammonium group as a cation). As a rule, however, the purely cationic, d. H. not zwitterionic structures proved to be more advantageous.

If the cationic group is an organically substituted ammonium or amine, one of the substituents is often the lipophilic group or contains the lipophilic group. As further organic substituents are often alkyl groups, for example methyl, ethyl or n- or i-propyl groups.

With such cationic groups undesirable compounds such as surfactants, but also anionic inorganic groups such as uranyl groups can be separated particularly well.

According to a further embodiment, the separation of the fluorinated organic compounds from contaminated fluids by means of a kit of the first and a second adsorbent component. The second adsorbent component, which is a solid adsorbent, is then additionally provided in step A). Furthermore, the method then comprises step C), in which the contacting of the fluid with the second adsorbent component takes place. According to the invention, it has been found that by means of the method according to this embodiment, namely by combining the solid adsorbent component with the first adsorbent component, even more selective separation of fluorinated organic compounds, in particular fluorinated or perfluorinated surfactants, is possible. For first adsorbent components that are not already adducted with the fluorinated compounds fail, is only by the addition of the second Adsorbenskomponente a

Separability achieved.

In step C) the contaminated fluid is brought into contact with the solid adsorbent component so that on the one hand the formed adduct of amphiphilic first adsorbent component and fluorinated organic compound and on the other hand also optionally present not bound to the first adsorbent component free fluorinated organic compound on the surface of the second adsorbent component can be bound.

According to a further embodiment, the method according to the invention is carried out such that step B) and C) are carried out simultaneously or that step B) is carried out before step C). From the theoretical ones described above

Basically, the adsorption of the fluorinated organic compound to be separated takes place first, followed by the adsorption of, in particular, not adsorbed off from the fluid of step C) on the solid adsorbent component. In this respect, it is already apparent from theoretical considerations that as a rule step B) should be carried out before step C). An implementation of step C) after step B) is less favorable, especially since there is the risk that the first adsorbent component already with the second

Adsorbent component has entered into interaction and thus an interaction with the fluorinated organic compound to be separated is difficult.

According to a further embodiment, the process according to the invention is carried out in such a way that a compound of the formula R ¹ -ELX, R ¹ -LEX or R ¹ -EX is provided as the first adsorbent component in step A). Here, R ^{1 represents} the lipophilic group, E the hydrophilic group, L a linker and X a reactive functional group. This reactive functional group X is chosen so that in step B) and / or step C) a chemical reaction with the Fluid enters or can form hydrogen bonds with this. Due to the fact that the contaminated fluid

is predetermined (often an aqueous liquid), the expert is already clear due to the simplest organic-chemical considerations, which functional groups are suitable for this purpose. The linker L can be any group that is not affected by the

Definition of the hydrophilic group, the lipophilic group and the reactive group is detected. For example, alkylene groups (for example CH ₂ or C ₂ H ₄ ) between E and X or ester or ether groups between R ¹ and E are conceivable.

According to a further embodiment, the functional group X, in particular in the case of an aqueous solvent, can have one, two or more hydroxyl groups. This supports the formation of hydrogen bonds to the fluid and at the same time increases the hydrophilicity of the hydrophilic group. An increase in the hydrophilicity may be advantageous in individual cases.

Furthermore, the functional group X may be chosen such that, in particular in the case of an aqueous solvent, one, two or more hydroxyl groups are formed by reaction with the fluid. Depending on the group and the environmental conditions, however, the duration of this reaction can far exceed the duration of the process according to the invention, so that at most partial conversion is to be assumed here. Thus, according to another embodiment, the functional group X can therefore be selected from epoxide groups and groups which react step B) and / or step C) in an S _N reaction to form a hydroxy group. As groups that are in an S _N -

Reaction to react a hydroxy group, are in particular 2-C hlorethanol groups, alkyl sulfonate groups, bromo-alkyl groups or iodo-alkyl groups mentioned.

According to a further embodiment, the first adsorbent component is chosen such that in the formula R ¹ -ELX, R ¹ -LEX or R ¹ -EX two or more groups X or XL are bonded to the hydrophilic group. It follows accordingly

in particular the formulas R ¹ -E- (LX _n ), R ¹ -E- (LX) _n , R ¹ -LEX _n or R ¹ -EX _n . In this case, n can then be two or three, but in the case of the first mentioned compound it can also be greater than 3; L and X can each be the same or different.

If several such groups X are present, then X can in each case be an ether group bonded via a methylene, ethylene or propylene linker, in particular ethyl or ethyl

Be methyl ether group. With such multiple substituents, the same effect as a single polyol substituent can be obtained.

Furthermore, as groups X, at least two alcohol groups or precursors from which alcohol groups can be formed by reaction with the fluid may be present. In particular, vicinal diol groups or precursor structures should be mentioned here.

According to a further embodiment, the functional group X of the first adsorbent component is selected so that it is time and process dependent

Properties can be adjusted, in particular in the form of a pH regulator. Thus, for example, in the case of S _N reactions of the group X with water in the case of 2-chloroethanol groups, alkyl sulfonate groups, bromo-alkyl groups and iodo-alkyl groups, mineral acids are liberated. This release takes place in situ, so that, for example, in the case of amines as a hydrophilic group, the "quaternization reagent" H ⁺ required for the quaternization of the nitrogen and the better adsorption of the fluorinated organic compound is generated locally. Furthermore, by changing the pH, the environmental conditions of an aqueous mixture to be purified can also be changed so that the interaction of the adduct of the first

Adsorbent component and fluorinated organic compounds on the one hand and second Adsorbenskomponente on the other hand be strengthened.

The embodiments of the above seven paragraphs do not relate exclusively to the case in which compounds of the formula R ¹ -ELX, R ¹ -LE-X or R ¹ -EX are provided as the first adsorbent component. They also apply in principle when compounds of the formula XLR ¹ -E or XR ¹ -E are present. However, it has proved to be advantageous if the reactive group X, by means of which, inter alia, the hydrophilicity can be increased, is not bound to the lipophilic but to the hydrophilic group.

According to a further embodiment, the first adsorbent component is chosen so that it has a particularly low aquatic toxicity. The generally well-suited quaternary non-polymeric alkylamines (for example hexadecyltrimethylammonium chloride, dioctyldimethylammonium chloride or quaternary cocoalkylmethylamine-ethoxylate methyl chloride) and chloroalkylamines (for example 3-chloro-2-hydroxypropyl-lauryl-dimethylammoniumchloride) often have a high aquatic toxicity and are according to C LP - Regulation 1 272/2008 very toxic to aquatic organisms. Aminopropyl esters and aminopropylamides (for example undecylamidopropyltrimethylammonium methosulfate, docosylamidopropyldimethylamine or 2-hydroxy-3-trimethylammoniumpropyldocosanoate), aminodipropionates (for example 3- [2-carboxy- ethyl (octyl) amino] propanoic acid or Natriumoctyliminodiproponiat), quaternary polymeric alkylamines (for example, the diquarernary polydimethylsiloxane Rewoquat SQ1 Evonik) already have a significantly lower toxicity. In terms of toxicity but most favorable are compound classes, which are used for example in hair shampoos or fabric softeners. These include betaines (for example the TEGO Betain F50 from Evonik) and in particular triethanol esterquats (for example dioleoylethylhydroxyethylmonium methosulphate or corresponding compounds in which the oleyl units are at least partially replaced by saturated C.sub.15 to C.sub.18-alkyl groups). According to a further embodiment, in step A) a solid Adsorbenskom- component is provided which has a nonionic surface. This is understood to mean a surface on which charges may temporarily be present, for example because it is an electrical conductor with graphite structural elements, but in which there are no permanent ionic centers on the surface. For example, activated carbon whose surface may be partially negatively charged, but which is known not to be a compound having an ionic structure.

The solid adsorbent component may in particular be a modified or

be unmodified adsorbent, selected from activated carbon, alumina, silica gels, carbon blacks, zeolites, silica gels, clays and fibrous or

microcrystalline celluloses (such as pearl celluloses). In order to achieve better adsorption of the adduct of fluorinated organic compound and first adsorbent component, the surface of the solid adsorbent component should be as lipophilic as possible. For this purpose, the abovementioned solid adsorbent components may be modified lipophilic; as an example, lipophilic modified aluminas and hydrophobically modified percelluloses may be mentioned.

In your capacity as a conventional solid adsorbent has the second

Adsorbent component preferably the largest possible specific surface area (which can be determined by means of DIN ISO 9277: 2003-05). As a rule, the specific surface area will be at least 10 ¹ m ² / g and in particular 5 * 10 ² to 5 * 10 ³ m ² / g, for example 9 * 10 ² to 1, 5 * 10 ³ m ² / g. According to a further embodiment, the second adsorbent component has an average particle diameter of 0.005 to 6 mm, in particular 0.02 to 4 mm, for example 0.05 to 1 mm. The particle size is determined by sieving. The particle shape can be arbitrary, for example, spherical or even needle-shaped. The form of the porosity of the adsorbent is arbitrary from macro to microporous.

According to a further embodiment, the method according to the invention is carried out in such a way that a flocculation aid is added before step D) (and usually also after step C) (in individual cases, however, the addition may also be concurrent with or before step B) and / or C, perhaps because the flocculation takes place only after adsorption of the contaminant). In principle, such a method is useful for very small particle sizes of the solid adsorbent component and advantageous for the larger surfaces associated with these particle sizes (thus the ranges mentioned in the preceding paragraph are valid, in particular with respect to the upper limit). Particularly suitable for this embodiment are adsorbents having average particle sizes of 0.005 mm to a maximum of 1 mm, for example up to a maximum of 0.5 mm particle diameter. As a rule, the solid adsorbent component is added in finely divided form to the contaminated fluid so that adsorption can take place. Subsequently, the loaded adsorbent kit with a

Flocculants added to flocculation. This results in pollutant-laden, larger flakes that sediment easily or float and / or can be separated by filtration. When suitable flocculants are selected, the amount of organofluorocompound separated can be further increased. As flocculants, for example, cationic, but especially anionic polyelectrolytes are suitable. These may be based on, for example, polyacrylate, polyacrylamide, polyethyleneimine and polyethylene oxide. In addition, nonionic synthetic and natural flocculants (for example starch and glue) or inorganic polymers such as polyaluminium compounds can also be used in combination with polyvalent, low molecular weight aluminum or iron salts. The use of the adsorbent kit according to the invention in combination with a flocculant has the advantage that the Organofluorverbindungen containing flocculation products (for example, PFT-containing flocculation products) usually very stable in their structure; The pollutant is then permanently immobilized in the flake and does not tend to wash out.

According to a further embodiment, the method according to the invention is carried out such that a nonionic surfactant is used in addition to the first adsorbent component, in particular together with the first adsorbent component and in particular in step B). By means of such a nonionic surfactant, stabilization of the adduct formed and / or stabilization of micelles formed can take place in certain combinations of first adsorbent component and organofluorine compound. As a result, an increase in efficiency can thus be achieved by such a cosurfactant. As nonionic surfactants (oligo), oxyalkylene compounds (for example fatty alcohol polyglycol ethers), carbohydrate compounds (for example alkyl polyglucosides, sucrose esters, sorbitan esters and fatty acid / V-methylglucamides) and amine oxides (for example

Alkyldimethylamine).

According to a further embodiment, the process according to the invention is carried out in a stirred reactor or under conditions which correspond to those in a stirred reactor. The process of the invention can bring its advantages particularly well under these conditions. It is according to the invention namely not necessary that the contaminated fluid is passed through a column with the adsorbents. Rather, it is sufficient if the two Adsorbenskomponenten is brought into contact with the fluid in any form and then carried a thorough mixing of Adsorbenskomponenten and fluid. Due to the strong interactions between fluorinated organic compound and adsorbent components such mixing, such as in a stirred reactor, completely sufficient to ensure good separation of the fluorinated organic compound. In order to allow a particularly fast separation, it may be useful, a

Add flocculant (which would not be required if used in a column or column). In principle, however, the process according to the invention can be carried out not only in a stirred reactor (in which the solid adsorbent component is frequently used in powder form) but also in a column or a fixed bed adsorber (in the case of the solid adsorbent component is often used in granular form).

The process according to the invention is described in more detail below, after the components of step A) have been prepared. First, the contaminated fluid from which fluorinated organic compounds are to be removed is treated with an amphiphilic, cationic additive (as first adsorbent component) with stirring (~ 100 rpm). To set a suitable hydrophobic-hydrophilic balance, a compound is provided which is provided with amino groups and / or quaternary ammonium groups and also for the liphohilen share with longer alkyl chains (eg., Cocoalkyl, stearyl or octyl or dodecyl ) Is provided. Functionalities such as aryl and benzyl groups also allow the desired interaction and formation of adducts with fluorinated organic compounds. The said aryl, aralkyl and alkyl groups may also be partially fluorinated. Typically, the total concentration of the fluorinated organic present in the fluid becomes

Compounds are between 0.001 and 100 mg / L; the concentration of added first adsorbent component will then usually be between 0, 1 and 1000 mg / L, often 1 to 100 mg / L. From concentrations of 0.2 mmol / L, often 1 to 10 mmol / L, the advantageous formation of micelles is to be expected depending on the first adsorbent component. Frequently, the concentration of the first adsorbent component will be equal to or higher than the expected concentration of the fluorinated organic compound to be separated, for example, at least 50 times to 1,000 times as high (by weight). From the interaction of the two components, at least in substantial parts, an adduct emerges, the stoichiometry of the adduct formed from the components being dependent on the concentration and the chemical structure of the reactants. The contact time can be a period of

Seconds to hours, often in the range of 1 to 30 minutes.

In step B), the fluid is brought into contact with the second adsorbent component so that the adduct formed, as well as fractions of still free pollutant and usually also the first adsorbent component, are bound to the second adsorbent component. Typically, this process takes place in a stirred reactor by reacting in the fluid (which was already provided with the first adsorbent component) the second

Adsorbent component, e.g. Powder coal is dispersed with stirring (about 1 00 rpm). The concentration of the incorporated solid adsorbent component is between 1 and 10000 mg / L, preferably between 10 and 1000 mg / L, the stirring time may in turn comprise a period of seconds to hours, often in the range of 1 to 30 minutes. Alternatively, the adsorbent may be present in an adsorption column and perfused with the contaminated fluid to achieve the desired adsorption.

The next step involves separating the purified fluid from the loaded adsorbent with the aid of a flocculant aid. This process of solid-liquid separation takes place in the stirred reactor; it is typically added flocculants in a concentration of 0.1 - 10 mg / L. It is stirred for several minutes (about 1 00 rpm).

Following this step, even if no flocculant is added, sedimentation is carried out without stirring. The sediment is separated via a filter device. If necessary, the fluid thus purified may be subjected to further treatment with an adsorbent or may also undergo the treatment according to the invention again.

The object of the invention is further achieved by a kit for separating fluorinated organic compounds from contaminated fluids. This kit comprises a first adsorbent component which is liquid or can be brought into a liquid form and a second (solid) adsorbent component. The first adsorbent component is a chemical compound containing a lipophilic group and a hydrophilic group or containing such a compound in dissolved form, wherein the hydrophilic group contains at least one cationic group and wherein the lipophilic group is selected from alkyl groups containing at least one octylene unit include aryl groups and aralkyl groups. In liquid form, this also means that this liquid form takes place only by dissolution in the fluid to be purified or by dissolution in any other solvent which is miscible with the fluid.

Further advantageous embodiments of the kit are explained above in the description of the method according to the invention. The object of the invention is finally also by using a

Compound of the formulas R ¹ -ELX, R ¹ -LEX or the formula R ¹ -EX for the separation of fluorinated organic compounds from contaminated fluids. Here, R ¹ , E, L and X are as defined above. For this purpose, further advantageous embodiments are explained above in the description of the method according to the invention.

The inventive method, the kit used for this purpose and also the compounds used as the first adsorbent component of the formulas R ¹ -ELX, R ¹ -LEX or the formula R ¹ -EX are particularly suitable for the separation of fluorinated organic compounds. Fluorinated hydrocarbons, such as perfluorinated compounds, partially fluorinated surfactants or perfluorinated surfactants, should be mentioned in particular.

Basically, it is also possible that a desorption of the adsorbed compounds (adduct) and thus a regeneration of the separation phase (activated carbon) and the recovery of the fluorinated compounds is possible, especially if this is recyclables, otherwise only with complex chemical reactions again would have to be made. Such a desorption can be carried out, for example, if weakly basic amino groups are present in the first adsorbent component and form adducts with anions of, for example, perfluorinated surfactants. The acid anions of the surfactants are reversibly bound and with an addition of base, the free amino groups are re-formed during regeneration. Depending on the type of amino group (primary, secondary or tertiary amino group) and on the constitution of the adduct, the pH of the optimal regeneration is dependent or adjustable.

In summary, it should be noted that the new process is specifically based on the state of the art and the modern practice of water treatment of PFT-contaminated waters and this through the use of specific

Carrier compounds (according to the invention: first Adsorbenskomponenten) improved. This allows commercial adsorbents and their established ways of

Use regeneration as well as the thermal reactivation of activated carbons and at the same time save both plant and process costs through a reduced use of materials. Further advantageous embodiments and developments of the invention will become apparent hereinafter - without limiting the generality - from the examples.

Adsorption in batch process:

In the following, the adsorption in the batch process will be explained and the efficiency of the adsorption method using different reagents will be shown. In this case, they are used in a four-stage or six-stage RRS plant (stirred reactor sorption plant).

The process steps include:

Stage 1 Dosage / Reagent 1: first adsorbent component

Step 2 Dosage / Reagent 2: second adsorbent component

Step 3 Dosage / Reagent 3: Flocculation Aid

Stage 4: sedimentation

Step 5 Dosage / Reagent 4: second adsorbent component

Stage 6 Sedimentation Depending on the example, the reagents used and the number of stages vary.

Each 800 ml PFT-containing raw water are measured with a measuring cylinder and placed in a 1000 ml beaker. In total, four samples are prepared. As PFT-containing raw water here is an aqueous mixture containing the following PFT used: perfluorooctane sulfonate (PFOS) 2.98 g / l, perfluoroheptane sulfonate (PFHpS) 0.27 g / l, perfluorohexane sulfonate (PFHxS) 3.90 g / l , Perfluorobutanesulfonate (PFBS) 0.54 g / l, perfluorooctanoic acid (PFOA) 0.36 g / l, perfluoroheptanoic acid (PFHpA) 0, 1 g / l,

Perfluorohexanoic acid (PFHxA) 0.64 g / l, perfluoropentanoic acid (PFPeA) 0.21 g / l,

Perfluorobutanoic acid (PFBA) 0.23 g / l.

The covered beakers are then placed in the batch mixer. Once the intended amount of first adsorbent component (reagent 1) has been supplied to the respective beaker, the stirring blade is immersed in the medium, the agitator is turned on and the speed is set to the intended value. The dosage of the second adsorbent component (reagent 2) and the

Flocculation aid (reagent 3) takes place in each case after expiry of the scheduled

Reaction times. The stirrer speed is thereby adapted specifically for the individual test phases. At the end of the third stage, the sedimentation phase begins. For this purpose, the stirrer is switched off and the stirring blades removed from the samples.

After the sedimentation time, the solids contained in the samples are separated by filtration. The filtrate is collected in 1 000 ml beakers and for the further analysis (PFT concentration) as small as possible sample volumes are removed. The stirring blades and stirrer shafts of the series agitator are cleaned again, if a further adsorption step (reagent 4) is subsequently carried out with the filtrate. After the second sedimentation time, the sediment contained in the sample solution is separated by filtration and the remaining filtrate is analyzed again. Example 1 a) Reagents Used:

Reagent 1: Preparation of 50 ml reagent solution 49.5 g distilled water and 0.5 g Quab 342 (40% aqueous solution of 3-chloro-2-hydroxy-propyldimethyldocecyl ammonium chloride, Quab C hemicals Inc., USA)

Reagent 2: powdered activated carbon based on hard coal (Cornelsen

Environmental technology, type: PFT Sorb, BET 900 m ² / g)

Reagent 3: Flocculant (from Ashland, type: Praestol A4030L) Preparation of a 0.1% flocculant aid dosing solution from 99.9 g of distilled water and 0.1 g of flocculant

Reagent 4: as reagent 2 b) process steps and settings:

Phase 1: Dosage of Reagent 1 1 ml / l each; Speed: 200 min ^-1 ;

Reaction time: 30 minutes

Phase 2: Dosing of reagent 2; Speed: 200 min ^-1 ; Reaction time: 30 minutes Approach no. 1 2 3 4

Reagent 2 [mg / l] 25 50 75 100

Phase 3: dosage of reagent 3 1 ml / l each; Speed: initially 200 min ^-1 after 1 minute 80 min ^-1 ; Reaction time: 1 5 minutes

Phase 4: sedimentation; Sedimentation time: 5 minutes

Phase 5: filtration; Filter type: folded filter Whatman 597 V2

Phase 6: Dosage of Reagent 4 Dosage of Reagent 1 25 ml / l each; Speed: 200 min ^-1 ; Reaction time: 30 minutes

Phase 7: filtration; Filter type: folded filter Whatman 597 V2

Example 2

The procedure is as in Example 1, except that the reagent 1 hydrolyzed 3-chloro-2-hydroxy-propyldimethyldocecylammoniumchlorid (degree of hydrolysis about

12 mol%) used.

Example 3

The procedure is as in Example 1, but is used as reagent 1 (I -Dodecyl) trimethylammonium chloride (Alfa Aesar). Example 4

The procedure is as in Example 1, however, as reagent 1 (I -tetradecyl) trimethylammonium chloride (Alfa Aesar) used.

Example 5 Experiment without first adsorbent component

The procedure is carried out as in Example 1; instead of reagent 1, the same amount of distilled water is added.

Comparison of Example 1 to 4 and Example 5 The comparison clearly shows how advantageous the method according to the invention is. Table 1 shows the residual concentration of PFT remaining in the filtrate after carrying out Experiments 1 to 5 in g / L (blank concentrations are indicated under concentration [Conc.] PFTsorb = 0): TABLE 1

FIG. 1 shows the graphic preparation of the results of the test series from Table 1. The activated carbon without the addition of the first adsorbent component (dashed line) shows the worst results. Example 1 (solid line) the best. By adding chloro-2-hydroxypropyldimethyldodecylammonium chloride, it is therefore possible to use significantly small amounts of adsorbent. Between these results are Example 2 (dash-dot line - ^■ -), Example 3 (dash-dot line - ^■ ) and Example 4

(dotted line). Figure 2 illustrates this statement again by plotting the efficiency achieved as a function of the ratio of adsorbent and PFT adsorptive.

Example 6 to 10 test series without first adsorbent component

The procedure is as in Example 5. Instead of powdered activated carbon another second adsorbent component is used in an amount of 100 mg / L. This is bone meal (Powdered bovine bone with a crude ash content of 81, 4% - Example 6), titanium dioxide (in powder form - Example 7), granular starch "Amylofax 75" AVEBE (Example 8), granular starch "Wisprofloc P" AVEBE (Example 9) and granular starch "Avecat 1 5" AVEBE (Example 1 0). In comparison to activated carbon, these have a more hydrophilic surface chemistry - resulting in lower efficiencies for PFT adsorption.

FIG. 3 shows the efficiencies achieved from Examples 1 and 5 to 10 in FIG

Dependence on the solid adsorbent component

Example 1 1 The procedure is carried out as in Example 1, but raw water with the

Ingredients used in accordance with the information given in Table 2 below. Furthermore, stages 3, 4 and 5 are omitted and in comparative experiments activated carbon 1 and 2 also stage 1. Finally, the adsorbent component 1 was used in an amount of 22.5 mg / l and the adsorbent component 2 in an amount of 100 mg / l. Table 2 shows in each case two associated column pairs, in which the left-hand column indicates the concentration of the respective PFT in the raw water and the right column indicates the quantities of these PFTs separated by the adsorbent components. It can be seen that a significantly better efficiency than with pure activated carbon can be achieved by the kit according to the invention. Table 2 (all values have the unit g / l)

RohAktivRohAktivRohQuab 342 water coal 1 water coal 2 water + activated carbon 2

PFBA 0.56 0.09 0.46 0, 1 8 0.65 0.52

PFPeA 1, 6 0.81 1, 4 1, 01 1, 9 1, 86

PFHxA 2.2 1, 88 2, 1 2.03 3 3

PFHpA 0.4 0.39 0.43 0.43 0.48 0.48

PFOA 0.87 0.87 0.8 0.8 0.92 0.92 PFBS 1, 00 0.90 0.96 0.96 1, 1 1, 1

PFHxS 6.40 6.35 4 4 7.6 7.6

PFOS 1 1 10.9 5.9 5.9 1 1 1 1

Total PFTs 24.03 22, 1 9 1 6.05 1 5.31 26.65 26.48

Efficiency 92.3% 95.4% 99.4%

Activated carbon 1 = Danube Carbon, Hydraffin P1 000

Activated carbon 2 = powdered activated carbon based on hard coal (Cornelsen

Environmental technology, type: PFT Sorb, BET 1000 m ² / g)

Example 1 The procedure is as in Example 1 1 (also with regard to the amounts of adsorbent components used), but raw water is used with the ingredients according to the information in Table 3 below. Furthermore, the stages 3, 4 and 5, in the comparative experiments activated carbon 1 to 3 additionally accounted for the level 1 and in the experiment "TEA esterquat" additionally level 2. Table 3 shows in the leftmost column, the concentration of the respective PFT im

Raw water and in the columns right next to the separated by the Adsorbenskomponenten amounts of these PFTs. One recognizes that already by the first

Adsorbent component without additional solid adsorbent almost the

Efficiency is achieved, which is also achieved by the kit according to the invention. When TEA-esterquat is used, the activated carbon can already be dispensed with because precipitation of the formed adduct can be observed after contacting this compound with the raw water. The TEA esterquat used is an oleic acid-based esterquat obtainable by the triplicate esterification of triethanolamine with unsaturated C18 fatty acids (oleic acid-based) followed by quaternization with dimethyl sulphate. The solubility is 4 mg / L (at 20 ° C and pH 7, 1); the melting point is 4 ° C and the density 1.059 g / cm ³ (at 20 ° C) The TEA ester quat is used as a solution in 2-propanol. In any case, both examples have a much better efficiency than can be achieved with pure activated carbon. In addition, it turns out that this effect is even more evident if one considers only the PFTs with 6 or fewer carbon atoms in the fluoroalkyl group. Table 3 (all values have the unit g / l)

Raw water ActiveActiveActaTEA-Esterquat coal 1 coal 2 coal 3 Esterquat + Activated carbon 2

PFBA 6.9 0.5 0.5 0.7 0.8 0.9

PFPeA 16 4 4 3 4 5

PFHxA 33 6 11 4 12 12

PFHpA 5.5 2.5 4.1 1.6 4.1 3.9

PFOA 12 6.8 10.4 4.1 10.5 10.5

PFNoA 0.13 0.09 0.13 0.06 0.12 0.12

PFDeA 0.09 0.09 0.09 0.07 0.09 0.09

PFOSA 0.62 0.56 0.62 0.33 0.58 0.59

PFBS 31 13 16 7 24.5 23.6

PFHxS 170 112 150 60 160.6 160.7

PFHpS 24 21.1 23.39 16.2 23.59 23.61

PFOS 500 447 487 350 475 486

4: 2 FTS 0.25 0.21 0.24 0.17 0.21 0.21

6: 2 FTS 25 19.5 23.7 10 20.7 20.4

8: 2 FTS 13 12.32 12.85 9.6 12.49 12.57

Total PFTs 837.49 645.67 744.01 466.83 749.28 760.19

Efficiency 77.1% 88.8% 55.7% 89.5% 90.8%

Total C4-C6 282.15 155.21 205.44 84.87 222.81 222.81

Efficiency 55.0% 72.8% 30.1% 79.0% 79.0% C4-C6 Activated carbon 3 = reagent 2

PFNoA = perfluorononanoic acid, PFDeA = perfluorodecanoic acid; PFOSA = perfluorooctanoic acid amide, n: 2 FTS = n: 2 fluorotelomer sulfonic acid C _n F _{2n + 1} C ₂ H ₄ S0 ₃ H

Example 1 Further compounds suitable as the first adsorbent component were investigated without the addition of a solid adsorbent component. As in the case of the TEA esterquat (Example 12), the addition of activated carbon can already be dispensed with because precipitation of the adduct formed can be observed after contacting these compounds with the raw water. If the TEA esterquat from Example 12 is replaced under otherwise identical test conditions by a solution of 80% dioleoylethylhydroxyethylmonium methosulfate in 20% glycol or alternatively by Tego Betain F 50 from Evonik (the alkylamidopropylbetaine: 1 -propanaminium-3-amino -N-carboxymethyl-N, N-dimethyl-N-C ₈ -C ₁₈ acyl derivative) as well as precipitation products are to be observed even when varying the raw waters used, depending on raw water and first

Adsorbent component was different in type (flake structure) and amount. In each case, visually discernible precipitates and a significantly reduced PFT residual concentration in the treated raw water showed.

Claims

claims

1 . Process for the separation of fluorinated organic compounds

Contaminated fluids by means of at least a first adsorbent component with the following steps

A) providing the first adsorbent component, wherein

the first adsorbent component is a chemical compound containing a lipophilic group and a hydrophilic group or containing such a compound in dissolved form,

wherein the hydrophilic group contains at least one cationic group, the lipophilic group being selected from alkyl groups comprising at least one octylene unit, aryl groups and aralkyl groups, and wherein the cationic group is an amine, an organo-substituted ammonium, an organo-substituted Phosphonium or a metal complex;

B) contacting the contaminated fluid with the first

adsorbent;

D) separation of the at least first adsorbent component with the

adsorbed fluorinated organic compounds from the fluid.

2. Method according to the preceding claim,

characterized in that

the separation of the fluorinated organic compounds from contaminated fluids by means of a kit of the first and a second adsorbent component, wherein

in step A) additionally the second adsorbent component is provided, wherein the second adsorbent component is a solid adsorbent

and wherein the method further comprises the step of:

C) contacting the fluid with the second adsorbent component.

3. Method according to the preceding claim,

characterized in that

Step B) and C) are performed simultaneously or that

Step B) is performed before step C). Method according to one of the preceding claims,

characterized in that

the first adsorbent component has the formula R ¹ -ELX, R ¹ -LEX or R ¹ -EX, wherein

R ^{1 is} the lipophilic group, E is the hydrophilic group, L is a linker and X is a reactive functional group which in step B) and / or step C) enters into a chemical reaction with the fluid or can form hydrogen bonds with it.

Method according to the preceding claim,

characterized in that

the reactive group X has one, two or more hydroxyl groups or by the reaction of the group X with the fluid one, two or more

Hydroxy groups are formed.

Method according to the preceding claim,

characterized in that

the group X is selected from epoxide groups and groups which react step B) and / or step C) in an S _N reaction to a hydroxy group, in particular 2-C hlorethanol groups, alkyl sulfonate groups, bromo-alkyl - Groups or iodo-alkyl groups.

Method according to one of the three preceding claims,

characterized in that

in the first adsorbent component of the formula R ¹ -ELX, R ¹ -LEX or R ¹ -EX two or more groups X or XL are attached to the hydrophilic group and X is in each case an ether bonded via a methylene, ethylene or propylene linker Group, especially ethyl or methyl ether group, or that

in the first adsorbent component of the formula R ¹ -ELX, R ¹ -LEX or R ¹ -EX, at least one group X or XL is attached to the hydrophilic group containing a vicinal diol group or a precursor for one by reaction with the fluid in step B) and / or step C) formed vicinal diol group.

8. Method according to one of the four preceding claims,

characterized in that

the reaction of the reactive group X with the fluid causes a change in the pH of the fluid.

9. Method according to the preceding claim,

characterized in that

the second adsorbent component provided in step A) has a nonionic surface.

1 0. A method according to any one of the preceding claims,

characterized in that

the second adsorbent component is selected from activated carbon,

Aluminas, silica gels, carbon blacks, zeolites, and fibrous or microcrystalline celluloses.

1 1. Method according to one of the preceding claims,

characterized in that

before step D) a flocculant is added.

1 2. The method according to any one of the preceding claims,

characterized in that

Step B) and Step C) in a stirred reactor or under conditions corresponding to those in a stirred reactor.

1 3. Kit for separating fluorinated organic compounds from contaminated fluids comprising a first adsorbent component and a second

Adsorbent component, wherein

the second adsorbent component is a solid adsorbent and

the first adsorbent component is a chemical compound containing a lipophilic group and a hydrophilic group or containing such a compound in dissolved form, the hydrophilic group containing at least one cationic group, the lipophilic group being selected from alkyl groups containing at least one octylene unit include, from aryl groups and aralkyl groups and wherein the cationic group comprises an amine, an organo-substituted ammonium, an organo-substituted phosphonium or a metal complex, and further wherein the first

Adsorbent component in particular either in dissolved form or is present as a liquid.

14. Kit according to the preceding claim, wherein in addition to the first and second Adsorbenskomponente a flocculant is included.

1 5. Use of a compound of the formulas R ¹ -ELX, R ¹ -LEX or the formula R ¹ - EX for the separation of fluorinated organic compounds from contaminated fluids, wherein

R ^{1 is} a lipophilic group selected from alkyl groups comprising at least one octylene moiety, aryl groups and aralkyl groups, E is a hydrophilic group containing at least one cationic group, said cationic group being an amine organic substituted ammonium, an organo-substituted phosphonium or a metal complex, L is a linker and

X is a reactive functional group that can undergo or hydrogen bond to the fluid with a chemical reaction.